CN102656518B - Photosensitive resin composition, dry film thereof, and printed wiring board formed using same - Google Patents

Abstract

Disclosed is an alkali-developable photosensitive resin composition which comprises a carboxylated urethane resin having a biphenyl novolak structure, a photopolymerization initiator, and aluminum hydroxide and/or a phosphorus compound. By further incorporating a heat-curable ingredient having a plurality of cyclic ether groups and/or cyclic thioether groups in the molecule, besides the ingredients described above, a photo- and heat-curable resin composition can be obtained. The photosensitive resin composition may further contain a colorant. By using the photosensitive resin composition or a dry film thereof, a printed wiring board having a flame-retardant cured coating film, such as a solder resist, formed from the halogen-free composition can be provided while imposing little burden on the environment, the cured coating film being flame-retardant and reduced in warpage and having various excellent properties including bendability, soldering heat resistance, and resistance to gold plating.

Description

Photosensitive polymer combination, its dry film and used their printed circuit board (PCB)

Technical field

The present invention relates to a kind of photosensitive polymer combination, described photosensitive polymer combination can form halogen-free composition and carrying capacity of environment few, there is the solder resist of anti-flammability and low warpage, bending property excellence.The invention still further relates to the dry film that has used described photosensitive polymer combination and the printed circuit board (PCB) with anti-flammability.

Background technology

In the past, printed circuit board (PCB) and flexible PCB (following, referred to as FPC) were required to have anti-flammability because being equipped on electronic device, and the solder resist of the part as them is also required to have anti-flammability.Wherein, FPC is generally polyimide substrate, is the film different from the printed circuit board (PCB) of glass epoxy substrate.But the thickness of the solder resist that should be coated with FPC due to printed circuit board (PCB) is identical, while being therefore the FPC of film, relatively the fire-retardant burden of solder resist becomes large.

Therefore, all the time, there are various motions for solder resist fire-retardant.For example; TOHKEMY 2007-10794 communique (patent documentation 1) has proposed the photosensitive polymer combination of the anti-flammability that a kind of FPC uses, the phosphorus-containing compound that it contains the optical polymerism compound in (a) binder polymer, (b) molecule with polymerisable ethylenic unsaturated bonds such as the halogenated aromatic rings such as bromophenyl and (methyl) acryloyl groups, (c) Photoepolymerizationinitiater initiater, (d) blocked isocyanate compounds and (e) has phosphorus atoms in molecule.But, from the viewpoint of carrying capacity of environment, preferably do not use the such halogen compounds of compound with halogenated aromatic ring and polymerisable unsaturated double-bond.

And then the printed base plate of the film of FPC representative is in the time of the photocuring of solder resist or heat curing, the warpage being caused by cure shrinkage is regarded as problem.

On the other hand, as halogen-free and there is the solder resist of anti-flammability, for example in TOHKEMY 2007-41107 communique (patent documentation 2), propose: to addition multi-anhydride in the reaction product of biphenyl phenolic resin varnish type epoxy resin and unsaturated monocarboxylic and the aqueous alkaline solution-soluble resin obtaining, contain as the biphenyl phenolic resin varnish type epoxy resin of hardening agent and the aqueous alkaline solution-soluble photosensitive polymer combination of Photoepolymerizationinitiater initiater, but be inadequate about low warpage and bendability.

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2007-10794 communique (claims)

Patent documentation 2: TOHKEMY 2007-41107 communique (claims)

Summary of the invention

the problem that invention will solve

Therefore, the object of the invention is to, a kind of use in printed circuit board photosensitive polymer combination can alkali developing is provided, it is that halogen-free composition and carrying capacity of environment are few, there is anti-flammability and low warpage, bending property excellence, as printed circuit board (PCB), particularly as TAB (tape automated bonding, the automatic combination of winding), COF (chip on film, cover brilliant film) etc. the solder resist of flexible PCB (FPC) use of representative be optimum, in addition, each characteristic such as hot, the resistance to gold-plated property of resistance to welding is also excellent.

The present invention also aims to, by using described photosensitive polymer combination, the dry film of each excellent such as low warpage and anti-flammability, bending property is provided and there is the printed circuit board (PCB) of the anti-flammability epithelium of such excellent specific property.

for the scheme of dealing with problems

In order to realize aforementioned object, according to the present invention, a kind of use in printed circuit board photosensitive polymer combination can alkali developing can be provided, it is characterized in that, its contain have xenol Novolac structure containing carboxyl urethane resin, Photoepolymerizationinitiater initiater and aluminium hydroxide and/or phosphorus-containing compound.

In a preferred embodiment, aforementioned containing carboxyl urethane resin be epoxy resin by making to have xenol Novolac structure react with monoacid the diol compound that obtains, with there is the diol compound of carboxyl, react with diisocyanate cpd obtain contain carboxyl urethane resin.In addition, aforementioned Photoepolymerizationinitiater initiater preferably comprises oxime ester compound.Other preferred embodiment in, by also contain Thermocurable composition outside aforementioned each composition, can make light solidifying/heat solidifying resin composition.Other preferred embodiment in, also contain colorant.Such photosensitive polymer combination can compatibly be used to form the solder resist of printed circuit board (PCB).

In addition, according to the present invention, can also provide a kind of aforementioned photosensitive polymer combination is coated on film and dry film dry and that obtain.And then according to the present invention, a kind of printed circuit board (PCB) can also be provided, it has the cured film that makes photocatalytic coating film be solidified into pattern-like and to obtain, wherein, described film is aforementioned photosensitive polymer combination to be coated on base material and the film that forms, or aforementioned photosensitive polymer combination is coated on film and the dry and dry film lamination that obtains on base material and the film forming.

the effect of invention

Photosensitive polymer combination of the present invention by contain have xenol Novolac structure containing carboxyl urethane resin, Photoepolymerizationinitiater initiater, aluminium hydroxide and/or phosphorus-containing compound, can form halogen-free composition and carrying capacity of environment few, there is all excellent epitheliums of each characteristics such as anti-flammability and low warpage, bending property excellence, hot, the resistance to gold-plated property of resistance to welding.Therefore, the photosensitive polymer combination of the application of the invention, can provide the dry film of each excellent such as low warpage and anti-flammability, bending property and have the printed circuit board (PCB) of solder resist epithelium such excellent specific property, anti-flammability.

Embodiment

The inventor etc. conduct in-depth research in order to realize aforesaid problem, found that: contain the photosensitive polymer combination containing carboxyl urethane resin, Photoepolymerizationinitiater initiater, aluminium hydroxide and/or phosphorus-containing compound with xenol Novolac structure and there is low warpage and bending property excellence and then anti-flammability and also have significant effect, thereby completed the present invention.From the problem points of conventional art, all realizing these characteristics is thrilling effects.

Below, for each constituent of photosensitive polymer combination of the present invention, be elaborated.

As in photosensitive polymer combination of the present invention, comprise have xenol Novolac structure containing carboxyl urethane resin, can compatibly use have that the have following formula epoxy resin of xenol Novolac structure of structure of (I) reacts with monoacid and the diol compound that obtains, with there is the diol compound of carboxyl, react with diisocyanate cpd and the resin that obtains.

(in formula, n represents mean value, is 1.01 ~ 5)

The epoxy resin with above-mentioned xenol Novolac structure is as NC-3000 (Nippon Kayaku K. K's manufacture) and commercially available.

Be not particularly limited as aforementioned monoacid; from can be to obtained viewpoint of giving photo-curable containing importing photonasty group (acryloyl group or methacryl) carboxyl urethane resin; preferably unsaturated monocarboxylic, particularly preferably has the monoacid of (methyl) acryloyl group.As concrete example; can list acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, β-acryloxy propionic, there is hydroxyalkyl (methyl) acrylate of 1 hydroxyl and 1 (methyl) acryloyl group and the reactant of dibasic acid anhydride, there is 1 hydroxyl and multifunctional (methyl) acrylate of multiple (methyl) acryloyl group and the reactant of dibasic acid anhydride; these monacid caprolactone modification things etc., can use these one kind or two or more.Wherein preferably acrylic acid, methacrylic acid etc. have the monoacid of (methyl) acryloyl group.

Wherein, in this manual, (methyl) acrylate is the term of being referred to as acrylate, methacrylate and their potpourri, is also same for other similar expression.

The aforementioned epoxy resin with xenol Novolac structure can adopt the method for reacting of known epoxy radicals and carboxyl in the past with monacid reaction.For example, under the existence of the such organic solvent of aftermentioned or under non-existence, under the existence of the polymerization inhibitor such as quinhydrones, oxygen, conventionally at approximately 50 ~ 150 ℃, react.Now as required, also can add the phosphorus compounds such as imidazolium compounds, triphenylphosphine such as the quaternary ammonium salt such as tertiary amine, triethyl benzyl ammonia chloride, 2-ethyl-4-methylimidazole such as triethylamine as catalyzer.

In addition, with respect to epoxy radicals 1 equivalent of epoxy resin with xenol Novolac structure, the preferred monacid acidic group of ratio (the input ratio of raw material) of the each composition in above-mentioned reaction is the ratio of 1.0 ~ 1.2 equivalents.

By make to have the epoxy resin of xenol Novolac structure react with monoacid the diol compound that obtains, with there is the diol compound of carboxyl, react with diisocyanate cpd, can obtain of the present invention have xenol Novolac structure containing carboxyl urethane resin.This urethane reaction can adopt known method in the past.Reaction can be carried out under the condition by being uniformly mixed at room temperature ~ 100 ℃ and at catalyst-free, in order to improve reaction velocity preference as being heated to approximately 70 ~ 100 ℃.In addition, with respect to isocyanate group 1 equivalent of diisocyanate cpd, total hydroxyl of the ratio of the each composition in above-mentioned reaction (the input ratio of raw material) preferred diol compound (epoxy resin with xenol Novolac structure is reacted and the diol compound obtaining and the diol compound with carboxyl with monoacid) is the ratio of 1.0 ~ 2.5 equivalents.The epoxy resin that preferably makes to have xenol Novolac structure reacts with monoacid and ratio that the equivalent proportion of the diol compound that obtains and the hydroxyl with the diol compound of carboxyl is 2:8 ~ 8:2.

As aforementioned have xenol Novolac structure use containing carboxyl urethane resin synthetic containing carboxylic diol compound, be not particularly limited, for example, can list polyol compound and the reaction product of multi-anhydride etc. that dihydromethyl propionic acid, dimethylolpropionic acid, 3 officials can be above.They can be used singly or in combination of two or more thereof.

As the aforementioned synthetic diisocyanate cpd using containing carboxyl urethane resin with xenol Novolac structure, can use known usual aromatic series or aliphatic diisocyanate compound.Among them, do not use the synthetic diisocyanate cpd of phosgenation (phosgene method) can reduce the halogen quantity of obtained resin, therefore preferred.And then, the viewpoint of the flexibility containing carboxyl urethane resin with xenol Novolac structure obtaining from lifting etc., further preferred aliphat isocyanates.As concrete example, for example, can list 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,12-ten dimethylene diisocyanates, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate etc.They can use separately, or combine two or more use.Among above-mentioned diisocyanate cpd, from the viewpoint of flexibility, particularly preferably use 2,4,4-trimethyl hexamethylene diisocyanate.

The aforementioned carboxyl urethane resin that contains with xenol Novolac structure has multiple carboxyls, the crosslinking points while therefore becoming heat curing on the side chain of trunk polymer.In addition, during as photosensitive composite, can utilize aqueous alkali to develop.

In addition, the aforementioned acid number containing carboxyl urethane resin with xenol Novolac structure is preferably the scope of 30 ~ 200mgKOH/g, the more preferably scope of 40 ~ 120mgKOH/g.From the viewpoint of alkali-developable, containing the acid number of carboxyl urethane resin during lower than 30mgKOH/g, can become and be difficult to alkali development, on the other hand, while exceeding 200mgKOH/g, there is the dissolving of developer solution to exposure portion, therefore, it is thinner than needed that line becomes, and is dissolved by the developing and peels off the portion of exposure sometimes and unexposed portion indistinction, be difficult to describe normal corrosion-resisting pattern, therefore not preferred.

In addition, aforementioned have xenol Novolac structure containing the weight-average molecular weight of carboxyl urethane resin according to resin matrix and difference is preferably 2000 ~ 150000 scope conventionally, more preferably 5000 ~ 100000 scope.Weight-average molecular weight was lower than 2000 o'clock, and thermotolerance is insufficient.On the other hand, weight-average molecular weight exceedes at 150000 o'clock, storage stability variation.

The compounding amount containing carboxyl urethane resin with xenol Novolac structure like this, being all preferably 5 ~ 60 quality % in composition, is preferably 10 ~ 50 quality %.When compounding rate is less than above-mentioned scope, coating strength reduces, therefore not preferred.On the other hand, during more than above-mentioned scope, the reduction such as viscosity uprises, coating, therefore not preferred.

As aforementioned Photoepolymerizationinitiater initiater, the oxime ester that can use choosing freely to have an oxime ester base is that Photoepolymerizationinitiater initiater, alpha-aminoacetophenone are Photoepolymerizationinitiater initiater, and acylphosphine oxide is in the group of Photoepolymerizationinitiater initiater composition a kind Photoepolymerizationinitiater initiater above.

It is the commercially available product of Photoepolymerizationinitiater initiater as oxime ester, can list CGI-325, IRGACURE (registered trademark) OXE01, IRGACURE OXE02 that Ciba Japan K.K manufactures, N-1919, ADEKA ARKLS NCI-831 etc. that ADEKA Corporation manufactures.In addition, also can compatibly use the Photoepolymerizationinitiater initiater in molecule with 2 oxime ester bases, particularly, can list the oxime ester compound with the represented carbazole structure of following general formula.

(in formula, X represents hydrogen atom, the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, phenyl, phenyl is (by the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, amino, alkyl amino or the dialkyl amido with the alkyl of carbon number 1 ~ 8 replace), naphthyl is (by the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, amino, alkyl amino or the dialkyl amido with the alkyl of carbon number 1 ~ 8 replace), Y, Z represents respectively hydrogen atom, the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, halogen group, phenyl, phenyl is (by the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, amino, alkyl amino or the dialkyl amido with the alkyl of carbon number 1 ~ 8 replace), naphthyl is (by the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, amino, alkyl amino or the dialkyl amido with the alkyl of carbon number 1 ~ 8 replace), anthryl, pyridine radicals, benzofuranyl (benzofuryl), benzothienyl (benzothienyl), Ar represents the alkylidene of carbon number 1 ~ 10, ethenylidene, phenylene, diphenylene, sub-pyridine radicals (pyridylene), naphthylene, thiophene, anthrylene (anthrylene), sub-thienyl (thienylene), furylidene (furylene), 2,5-pyrroles-bis-base, 4,4 '-talan-bis-base, 4,2 '-styrene-bis-base, n represents 0 or 1 integer.)

The particularly preferably X in aforementioned formula, Y is respectively methyl or ethyl, and Z is methyl or phenyl, and n is that 0, Ar is phenylene, naphthylene, thiophene or sub-thienyl.

With respect to aforementioned, containing carboxyl urethane resin 100 mass parts, such oxime ester is that the compounding amount of Photoepolymerizationinitiater initiater is preferably 0.01 ~ 5 mass parts.During lower than 0.01 mass parts, the photo-curable deficiency on copper, film can be peeled off and the coating characteristic such as chemical proofing reduces.On the other hand, while exceeding 5 mass parts, the light absorption of welding resistance film coated surface becomes acutely, the tendency that exists deep curability to reduce.More preferably 0.5 ~ 3 mass parts.

Be Photoepolymerizationinitiater initiater as alpha-aminoacetophenone, particularly, can list 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino acetophenone etc.As commercially available product, can list the IRGACURE-907 that Ciba Japan K.K manufactures, IRGACURE-369, IRGACURE-379 etc.

Be Photoepolymerizationinitiater initiater as acylphosphine oxide; particularly; can list 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4; 6-trimethylbenzoyl)-phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide etc.As commercially available product, can list the Lucirin TPO that BASF CORPORATION manufactures, the IRGACURE-819 that Ciba Japan K.K manufactures etc.

With respect to aforementioned, containing carboxyl urethane resin 100 mass parts, these alpha-aminoacetophenones are that Photoepolymerizationinitiater initiater, acylphosphine oxide are that the compounding amount of Photoepolymerizationinitiater initiater is preferably 0.01 ~ 15 mass parts.During lower than 0.01 mass parts, the similarly photo-curable deficiency on copper, film can be peeled off and the coating characteristic such as chemical proofing reduces.On the other hand, while exceeding 15 mass parts, cannot obtain the reduction effect of exhaust, and then the light absorption of welding resistance film coated surface becomes acutely, the tendency that exists deep curability to reduce.More preferably 0.5 ~ 10 mass parts.

As other Photoepolymerizationinitiater initiaters applicable to photosensitive polymer combination of the present invention, light-initiated auxiliary agent and sensitizer, can list benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthones compound, ketal compound, benzophenone cpd, tertiary amine compound and xanthone compound etc.

As benzoin compound, particularly, for example, can list benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether etc.

As acetophenone compound, particularly, for example, can list acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone etc.

As anthraquinone compounds, particularly, for example, can list 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone etc.

As thioxanthones compound, particularly, for example, can list 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, CTX, 2,4-diisopropyl thioxanthones etc.

As ketal compound, particularly, for example, can list acetophenone dimethyl ketal, benzil dimethyl ketal etc.

As benzophenone cpd, particularly, for example, can list benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4 '-methyldiphenyl thioether, 4-benzoyl-4 '-ethyl diphenyl sulfide, 4-benzoyl-4 '-propyl group diphenyl sulfide etc.

As tertiary amine compound, particularly, for example can list ethanolamine compound, there is the compound of dialkylamino benzene structure, in commercially available product, for example can list 4, 4 '-dimethylamino benzophenone (the NIS SOCURE MABP that Japanese Cao Da company manufactures), 4, the dialkylamino benzophenone such as 4 '-lignocaine benzophenone (EAB that Hodogaya Chemical Co.LTD. manufactures), 7-(lignocaine)-4-methyl-2H-1-chromen-2-ones (7-(lignocaine)-4-methylcoumarin) etc. are containing the coumarin compound of dialkylamino, 4-dimethyl ethyl aminobenzoate (KAYACURE (registered trademark) EPA that Nippon Kayaku K. K manufactures), 2-dimethyl ethyl aminobenzoate (the Quantacure DMB that International Bio-Synthetics company manufactures), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (the Quantacure BEA that International Bio-Synthetics company manufactures), p-(dimethylamino)-benzoic acid isopentyl ethyl ester (the KAYACURE DMBI that Nippon Kayaku K. K manufactures), 4-dimethylaminobenzoic acid 2-Octyl Nitrite (Esolol 507 that Van Dyk company manufactures), 4, 4 '-lignocaine benzophenone (Hodogaya Chemical Co.LTD. manufactures EAB) etc.

Among these, preferably thioxanthones compound and tertiary amine compound.From the viewpoint of deep curability, particularly preferably comprise thioxanthones compound.Wherein, preferably contain 2,4-dimethyl sulphur-based thioxanthones, 2,4-diethyl thioxanthone, CTX, 2, the thioxanthones compounds such as 4-diisopropyl thioxanthones.

With respect to aforementioned, containing carboxyl urethane resin 100 mass parts, the compounding amount of this thioxanthones compound is preferably below 20 mass parts.When the compounding amount of thioxanthones compound exceedes 20 mass parts, thick film curability reduces and the cost of goods increases.More preferably below 10 mass parts.

In addition, as tertiary amine compound, preferably there is the compound of dialkylamino benzene structure, wherein, coumarin compound and coumarin ketone (ketocoumarin) class containing dialkylamino that particularly preferably dialkylamino benzophenone cpd, maximum absorption wavelength are 350 ~ 450nm.

As dialkylamino benzophenone cpd, 4,4 '-lignocaine benzophenone because of toxicity low preferably.Because the maximum absorption wavelength containing the coumarin compound of dialkylamino is in the ultraviolet range of 350 ~ 410nm, therefore can provide painted less, water white photosensitive composite is mathematical, and the painted soldering-resistance layer of the color that reflects coloring pigment itself while having used coloring pigment also can be provided.Consider particularly preferably 7-(lignocaine)-4-methyl-2H-1-chromen-2-one from the viewpoint of the sensitization effect of the laser display excellence to wavelength 400 ~ 410nm.

With respect to aforementioned, containing carboxyl urethane resin 100 mass parts, the compounding amount of this tertiary amine compound is preferably 0.1 ~ 20 mass parts.The compounding amount of tertiary amine compound is during lower than 0.1 mass parts, and existence can not obtain the tendency of sufficient sensitization effect.On the other hand, while exceeding 20 mass parts, the surperficial light absorption of the dry welding resistance film that tertiary amine compound causes becomes violent, the tendency that exists deep curability to reduce.More preferably 0.1 ~ 10 mass parts.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can use separately or use as potpourri of more than two kinds.

With respect to aforementioned have xenol Novolac structure containing carboxyl urethane resin 100 mass parts, the total amount of such Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer is preferably below 35 mass parts.While exceeding 35 mass parts, the tendency that exists these light absorption to cause deep curability to reduce.

It is Photoepolymerizationinitiater initiater that photosensitive polymer combination of the present invention particularly preferably uses oxime ester.Its effect is not only in a small amount of situation, can obtain sufficient light sensitivity, and because the volatilization of the Photoepolymerizationinitiater initiater when the heat curing and in the after heat operation in the time of installation is few, therefore can suppress the contraction of cured coating film, thereby can make warpage reduce significantly.

In addition; acylphosphine oxide is that the deep curability of the use of Photoepolymerizationinitiater initiater while making light reaction promotes; and then the phosphorus-containing compound ftractureing by irradiation, derive from initiating agent is become to divide into groups into solidfied material network (network); thereby can improve efficiently the phosphorus concentration in cured coating film, make the further lifting of anti-flammability become possibility.

It should be noted that, foregoing Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer are owing to absorbing specific wavelength, and according to circumstances light sensitivity is understood step-down sometimes, thereby works as ultraviolet light absorber.But these are not only for the object of the light sensitivity that improves composition and use.The light that can absorb as required specific wavelength, improves surperficial photoreactivity, makes that the wire shaped of resist and opening are changed to vertically, cone-shaped, back taper shape, and can improve the machining precision of live width, opening diameter.

For photosensitive polymer combination of the present invention; using oxime ester is that Photoepolymerizationinitiater initiater, acylphosphine oxide are that any of Photoepolymerizationinitiater initiater is all effective; from promoting the wire shaped of resist as described above and the balance of opening, machining precision; and then promote the viewpoints such as low warpage properties, bending property, anti-flammability and set out, and be that Photoepolymerizationinitiater initiater and acylphosphine oxide are that Photoepolymerizationinitiater initiater is preferred with oxime ester.

As aforementioned aluminium hydroxide, can use general known aluminium hydroxide, Higilite series, HW, H21, H31, H32, H42M, the H43M etc. that for example can use Showa Denko K. K to manufacture.In addition, because the particle diameter of aluminium hydroxide is carefully effective to folding resistance, therefore from the anti-flammability of obtained cured film, the viewpoint of bending property, preferably use the aluminium hydroxide that carries out following processing: reinstate the dispersions such as bowl mill with solvent, resin one in advance and be machined to primary particle size, again with filtering (filtering) etc. more than filtering screening to 3 μ m, more preferably more than filtering screening to 1 μ m.

With respect to aforementioned, containing carboxyl urethane resin 100 mass parts, the compounding amount of these aluminium hydroxide it is desirable to the scope of 0 ~ 300 mass parts, is preferably 0 ~ 200 mass parts, more preferably 0 ~ 150 mass parts, more preferably 10 ~ 120 mass parts.While exceeding 300 mass parts, cannot obtain bending property fully.

Photosensitive polymer combination of the present invention preferably comprises phosphorus-containing compound.As phosphorus-containing compound, can be as organic phosphorus flame retardant and usual known phosphorus-containing compound has the compound shown in phosphate and condensed phosphoric acid esters, cyclic phosphazene compound, phosphonitrile oligomer or following general formula (II).

(in formula, R ¹, R ²and R ³represent independently respectively halogen atom substituting group in addition.)

As the commercially available product of the phosphorus-containing compound shown in above-mentioned general formula (II), there are HCA, SANKO-220, M-ESTER, HCA-HQ (being the trade name of Sanko Co., Ltd.) etc.

As phosphorus-containing compound that use in the present invention, particularly preferred, can list and have as the acrylate-based phosphorus-containing compound of reactive group, the phosphorus-containing compound with phenolic hydroxyl group, oligomer or polymkeric substance, phosphonitrile oligomer, phosphinates etc.

(methyl) acrylate of phosphorus element-containing can be to have the compound in P elements and molecule with multiple (methyl) acryloyl group, particularly, can list the R in aforementioned formula (II) ¹and R ²for hydrogen atom, R ³for the compound of (methyl) acrylate derivative.Conventionally can synthesize by the Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and known usual multifunctional (methyl) acrylate monomer.

As above-mentioned known usual (methyl) acrylate monomer, can list the diacrylate class of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; The multicomponent methacrylate class of the polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, three-hydroxyethyl isocyanuric acid ester or these ethylene oxide adducts, propylene oxide adduct or caprolactone addition product etc.; The multicomponent methacrylate class of oxirane or the propylene oxide adduct etc. of phenoxy group acrylate, bisphenol a diacrylate and these phenols; And the multicomponent methacrylate class of the glycidol ether such as urethane acrylate class of above-mentioned polyalcohols, glycerine diglycidyl ether, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl ether isocyanuric acid ester; And melamine acrylate and/or each methyl acrylic ester corresponding with aforesaid propylene acid esters etc.

Hydrophobicity, the thermotolerance with the phosphorus-containing compound of phenolic hydroxyl group are high, can not reduce because hydrolysis causes electrical characteristics the hot height of resistance to welding.In addition, as applicable combination, in the case of having used the epoxy resin in heat-curing resin, owing to being entered in network by group with epoxy reaction, therefore can obtain the advantage that can not ooze out after solidifying.As commercially available product, there is the HCA-HQ of Sanko Co., Ltd.'s manufacture etc.

As the phosphorus-containing compound of oligomer or polymkeric substance, because the reduction of the impact bending property of alkyl chain is few, and molecular weight is large, therefore can obtain the advantage that can not ooze out after solidifying.As commercially available product, the phosphorous Vylon 337 of company's manufacture etc. is spun in M-Ester-HP, the Dongyang that has Sanko Co., Ltd. to manufacture.

As phosphonitrile oligomer, phenoxy phosphazene compound is effectively, the ring of substituted or non-substituted phenoxy phosphazene oligomer or 3 aggressiveness, 4 aggressiveness, 5 aggressiveness, and the material of liquid state, pressed powder, all can compatibly use.As commercially available product, there is (Co., Ltd.) volt to see FP-100, FP-300, the FP-390 etc. of pharmacy manufacturing.Wherein, the phenoxy phosphazene oligomer being replaced by alkyl or hydroxyl, cyano group isopolarity group, high containing the dissolubility in carboxy resin, even if add in a large number, does not have the bad phenomenon such as recrystallization yet, therefore preferred.

In addition, by using phosphinates, can promote anti-flammability and do not lose cured coating film flexibility.By using the phosphinates of such excellent heat resistance, the oozing out of the fire retardant in the hot pressing can suppress to install time.As commercially available product, can list EXOLIT OP 930, EXOLIT OP 935 etc. that Clariant (Japan) K.K. manufactures.

With respect to aforementioned have xenol Novolac structure containing carboxyl urethane resin 100 mass parts, it is desirable to the scope of 0 ~ 200 mass parts as the compounding amount of the phosphorus-containing compound of these fire retardants, more preferably 0 ~ 100 mass parts, more preferably 10 ~ 80 mass parts.During with more than this scope a large amount of compounding of amount, the variation such as the bending characteristic of the cured film obtaining, therefore not preferred.

In order to give thermotolerance, can further in photosensitive polymer combination of the present invention, add Thermocurable composition.As Thermocurable composition used in the present invention, can use the known usual heat-curing resins such as blocked isocyanate compounds, amino resins, maleimide compound, benzoxazine colophony, carbodiimides resin, cyclic carbonate compound, multi-functional epoxy compound, multifunctional oxetane compound, episulfide resin.Among these, preferred heat curing composition is the Thermocurable composition in 1 molecule with multiple ring-type ethers and/or cyclic thioether base (following, referred to as ring-type (sulphur) ether).For the Thermocurable composition with these ring-types (sulphur) ether, just a lot of in commercially available kind, can give various characteristic according to its structure.

The Thermocurable composition in such molecule with multiple ring-types (sulphur) ether is the compound in molecule with any or 2 kinds of groups of the ring-type ether of 3 rings, 4 rings or 5 rings or cyclic thioether base, for example can list the compound in molecule with multiple epoxy radicals is multi-functional epoxy compound, the compound in molecule with multiple oxetanyls is multifunctional oxetane compound, and the compound in molecule with multiple thioether groups is episulfide resin etc.

As aforementioned multi-functional epoxy compound, for example, can list Japan Epoxy Resins Co., the j ER (registered trademark) 828 that Ltd. manufactures, jER834, jER 1001, jER 1004, the EPICLON (registered trademark) 840 that DIC Corporation manufactures, EPICLON 850, EPICLON 1050, EPICLON 2055, Dongdu changes into Epo Tohto (registered trademark) YD-011 that company manufactures, YD-013, YD-127, YD-128, the D.E.R.317 that The Dow Chemical Company manufactures, D.E.R.331, D.E.R.661, D.E.R.664, the Aral dite 6071 that Ciba Japan K.K. manufactures, Aral dite 6084, Aral dite GY250, Aral dite GY260, the Sumiepoxy ESA-011 that Sumitomo Chemical Co. Ltd. manufactures, ESA-014, ELA-115, ELA-128, the A.E.R.330 that industrial group of Asahi Chemical Industry manufactures, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A type epoxy resin, Japan Epoxy Resins Co., Ltd. the jERYL903 manufacturing, EPICLON 152, EPICLON 165 that DIC Corporation manufactures, Dongdu changes into Epo Tohto YDB-400, the YDB-500 that company manufactures, the D.E.R.542 that The Dow Chemical Company manufactures, the Araldite8011 that Ciba Japan K.K. manufactures, Sumiepoxy ESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. manufactures, A.E.R.711, A.E.R.714 etc. (the being trade name) brominated epoxy resin that industrial group of Asahi Chemical Industry manufactures, Japan Epoxy Resins Co., Ltd. the jER152 manufacturing, jER154, the D.E.N.431 that The Dow Chemical Company manufactures, D.E.N.438, the EPICLON N-730 that DIC Corporation manufactures, EPICLONN-770, EPICLON N-865, Dongdu changes into the Epo Tohto YDCN-701 that company manufactures, YDCN-704, the Araldite ECN1235 that Ciba Japan K.K. manufactures, Aral dite ECN1273, Aral dite ECN1299, Araldite XPY307, the EPPN (registered trademark)-201 that chemical drug company of Japan manufactures, EOCN (registered trademark)-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H, the Sumiepoxy E SCN-195X that Sumitomo Chemical Co. Ltd. manufactures, E S CN-220, the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry manufactures, ECN-299 etc. (being trade name) phenolic resin varnish type epoxy resin, the EPICLON 830 that DIC Corporation manufactures, Japan Epoxy Resins Co., Ltd. the jER807 manufacturing, (the being trade name) bisphenol f type epoxy resins such as Dongdu changes into Epo Tohto YDF-170, YDF-175, the YDF-2004 that company manufactures, the Aral dite XPY306 that Ciba Japan K.K. manufactures, Dongdu changes into the bisphenol-A epoxy resin such as Epo Tohto ST-2004, ST-2007, ST-3000 (trade name) that company manufactures, Japan Epoxy Resins Co., Ltd. the jER604 manufacturing, Dongdu changes into the Epo Tohto YH-434 that company manufactures, the Araldite MY720 that Ciba Japan K.K. manufactures, (the being trade name) glycidyl amine type epoxy resins such as the Sumiepoxy ELM-120 that Sumitomo Chemical Co. Ltd. manufactures, the hydantoins type epoxy resin such as the Araldite CY-350 (trade name) that Ciba JapanK.K. manufactures, DAICEL CHEMICAL INDUSTRIES, the CELLOXIDE (registered trademark) 2021 that LTD. manufactures, (the being trade name) alicyclic epoxy resins such as Araldite CY175, the CY179 that Ciba Japan K.K. manufactures, Japan Epoxy Resins Co., the YL-933 that Ltd. manufactures, (being trade name) trihydroxy benzene methylmethane type epoxy resin such as T.E.N., EPPN-501, EPPN-502 that The Dow Chemical Company manufactures, Japan Epoxy Resins Co., di-cresols type or united phenol-type epoxy resin or their potpourri such as YL-6056, YX-4000, YL-6121 (being trade name) that Ltd. manufactures, the bisphenol-s epoxy resins such as the EXA-1514 (trade name) that EPX-30, the DIC Corporation that EBPS-200, the ADEKA Corporation that chemical drug company of Japan manufactures manufactures manufactures, Japan Epoxy Resins Co., the bisphenol-A phenolic varnish type epoxy resin such as the jER157S (trade name) that Ltd. manufactures, Japan Epoxy Resins Co., the jERYL-931 that Ltd. manufactures, Aral dite 163 grade (being trade name) the four hydroxyphenyl ethane type epoxy resin that Ciba Japan K.K. manufactures, the Araldite PT 810 that Ciba Japan K.K. manufactures, the hetero ring type epoxy resin such as the TEPIC (registered trademark) that daily output chemical industrial company manufactures, the o-phthalic acid diglycidyl ester resins such as BLEMMER (registered trademark) DGT that Nof Corp. manufactures, Dongdu changes into four glycidyl group dimethylbenzene acyl group ethane (the tetraglycidyl xylenoyl ethane) resins such as the ZX-1063 of company's manufacture, ESN-190, ESN-360 that chemical company of Nippon Steel manufactures, DIC Corporation manufactures the epoxy resin containing naphthyl such as HP-4032, EXA-4750, EXA-4700, HP-7200, the HP-7200H etc. that DIC Corporation manufactures has epoxy resin, EXA-4816, EXA-4822, the soft tough epoxy resin of EXA-4850 series of bicyclopentadiene skeleton, it is epoxy resin that grease society of Japan manufactures the glycidyl methacrylate copolymerization such as CP-50S, CP-50M, and the copolymerization epoxy resin of N-cyclohexylmaleimide and glycidyl methacrylate etc., but be not limited to these.These epoxy resin can be used alone or in combination of two or more kinds.Among these, particularly preferably biphenyl phenolic resin varnish type epoxy resin, di-toluene phenol-type epoxy resin or their potpourri.

As aforementioned multifunctional oxetane compound, can list two [(3-methyl-3-oxetanes ylmethoxy) methyl] ether, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] ether, 1, two [(3-methyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, acrylic acid (3-methyl-3-oxetanyl) methyl esters, acrylic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters, their the multifunctional oxetanes class such as oligomer or multipolymer, and oxa-cyclobutanol and novolac resin, poly-(4-Vinyl phenol), cardo type bisphenols, calixarene kind, resorcinol calixarenes (calix resorcin arene) class or silsesquioxane (silsesquioxane) etc. have the etherate of the resin of hydroxyl etc.In addition, also can list and there is the unsaturated monomer of oxetanes ring and the multipolymer of (methyl) alkyl acrylate etc.

As the episulfide resin in aforementioned molecule with multiple cyclic thioether bases, for example can list Japan Epoxy Resins Co., YL7000 (bisphenol A-type episulfide resin), Toto Kasei KK that Ltd. manufactures manufacture YSLV-120TE etc.In addition, also can use and adopt same synthetic method that the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin is replaced to episulfide resin that sulphur atom forms etc.

With respect to aforementioned carboxyl 1 equivalent containing carboxyl urethane resin, the compounding amount in aforementioned molecule with the Thermocurable composition of multiple ring-types (sulphur) ether preferably reaches the scope of 0.6 ~ 2.5 equivalent, more preferably reaches the scope of 0.8 ~ 2.0 equivalent.In molecule, there is the compounding amount of Thermocurable composition of multiple ring-types (sulphur) ether lower than 0.6 o'clock, in soldering-resistance layer, have carboxyl residual, the reductions such as thermotolerance, alkali resistance, electrical insulating property, therefore not preferred.On the other hand, while exceeding 2.5 equivalent, low-molecular-weight ring-type (sulphur) ether can remain in dry coating, thereby makes to be coated with the reductions such as film strength, therefore not preferred.

In addition, as other Thermocurable composition that can compatibly use, can list the amino resins such as melamine derivative, benzoguanamine derivant.For example there are melamine methylol compound, methylol benzoguanamine compound, methylol glycoluril compounds and hydroxymethyl urea compound etc.And then alkoxy methyl melamine compound, alkoxy methyl benzoguanamine compound, alkoxy methyl glycoluril compounds and alkoxy methyl urea compounds can obtain by the methylol of melamine methylol compound, methylol benzoguanamine compound, methylol glycoluril compounds and hydroxymethyl urea compound is transformed to respectively to alkoxy methyl.To the kind of this alkoxy methyl, there is no particular limitation, for example, can be methoxy, ethoxyl methyl, propoxyl group methyl, butoxymethyl etc.Be particularly preferably the melamine derivative below 0.2% to human body, eco-friendly formalin concentration.

As these commercially available products, for example can list CYMEL (registered trademark) 300, with 301, with 303, with 370, with 325, with 327, with 701, with 266, with 267, with 238, with 1141, with 272, with 202, with 1156, with 1158, with 1123, with 1170, with 1174, same UFR65, (be Mitsui Cyanamide Co. above with 300, Ltd. manufacture), NIKALAC (registered trademark) Mx-750, same Mx-032, same Mx-270, same Mx-280, same Mx-290, same Mx-706, same Mx-708, same Mx-40, same Mx-31, same Ms-11, same Mw-30, same Mw-30HM, same Mw-390, same Mw-100LM, same Mw-750LM (is SANWA Chemical Co. above, Ltd. manufacture) etc.

Above-mentioned Thermocurable composition can use separately, or and uses two or more.

In addition, in order to promote the obdurability of curability and the cured film that obtains of composition, can be to the compound that adds 1 molecule in photosensitive polymer combination of the present invention and have multiple isocyanate group or end-blocking isocyanate group.The compound in 1 molecule like this with multiple isocyanate group or blocked isocyanate base can list in 1 molecule, there is the compound of multiple isocyanate group, i.e. polyisocyanate compound, or in 1 molecule, there is the compound of multiple blocked isocyanate bases, i.e. blocked isocyanate compounds etc.

As aforementioned polyisocyanate compound, can use for example aromatic polyisocyanate, aliphatic polyisocyante or ester ring type polyisocyanates.As the object lesson of aromatic polyisocyanate, can list 4,4 '-'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene diisocyanate, m xylene diisocyanate and 2,4-toluene diisocyanate dimer.As the object lesson of aliphatic polyisocyante, can list tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and isophorone diisocyanate.As the object lesson of ester ring type polyisocyanates, can list bicycloheptane triisocyanate.Also can list addition product, biuret body and the isocyanuric acid ester body of previously mentioned isocyanate compound.

In blocked isocyanate compounds contained blocked isocyanate base be isocyanate group protected by reacting with sealer, temporarily by the group of deactivation.In the time being heated to the temperature of regulation, this sealer dissociates, and generates isocyanate group.

As blocked isocyanate compounds, can use the addition reaction product of isocyanate compound and isocyanate-terminated dose.As the isocyanate compound that can react with end-capping reagent, can list chlorinated isocyanurates type, biuret type, addition product type etc.As this isocyanate compound, can use for example aromatic polyisocyanate, aliphatic polyisocyante or ester ring type polyisocyanates.As the object lesson of aromatic polyisocyanate, aliphatic polyisocyante, alicyclic polyisocyanates, can list above illustrative compound.

As isocyanate-terminated dose, for example can list the phenol such as phenol, cresols, xylenol, chlorophenol and ethyl-phenol is end-capping reagent; The lactams such as epsilon-caprolactams, δ-valerolactam, butyrolactam, azetidinone are end-capping reagent; Ethyl acetoacetate and diacetone isoreactivity methylene base system end-capping reagent; The alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzylic ether, methyl glycollate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate are end-capping reagent; The oximes such as formaldoxime, acetaldoxime, acetoxime (acetoxime), methyl ethyl ketoxime, diacetyl monoxime, cyclohexanone-oxime are end-capping reagent; The mercaptan such as butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, benzenethiol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol are end-capping reagent; The acid amides such as acetamide, benzamide is end-capping reagent; The imide series such as succinimide and maleimide end-capping reagent; The amine such as xylidin, aniline, butylamine, dibutylamine are end-capping reagent; The imidazoles such as imidazoles, 2-ethyl imidazol(e) are end-capping reagent; The imines such as methylene imine and propylidene imines are end-capping reagent etc.

Blocked isocyanate compounds can be commercially available product, for example can list Sumidule (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2265 is (above by Sumika Bayer Urethane Co., Ltd. manufacture, trade name), CORONATE (registered trademark) 2512, CORONATE 2513, CORONATE 2520 (is manufactured by Japanese polyurethane industrial group above, trade name), B-830, B-815, B-846, B-870, B-874, B-882 is (above by MIT SUI TAKEDA CHEMICAL S, INC. manufacture, trade name), TPA-B 80E, 17B-60PX, E402-B 80T (is manufactured by Asahi Kasei Chemicals Corporation above, trade name) etc.In addition, Smudule BL-3175, BL-4265 are the materials that uses Methylethyl oxime to obtain as end-capping reagent.

The compound in above-mentioned 1 molecule with multiple isocyanate group or end-blocking isocyanate group can use separately a kind, or combines two or more use.

With respect to aforementioned, containing carboxyl urethane resin 100 mass parts, the compounding amount in 1 such molecule with the compound of multiple isocyanate group or end-blocking isocyanate group is preferably the ratio of 1 ~ 100 mass parts, the more preferably ratio of 2 ~ 70 mass parts.Lower than 1 mass parts in the situation that, cannot obtain the obdurability of sufficient film in aforementioned compounding amount, therefore not preferred.On the other hand, in the situation that exceeding 100 mass parts, storage stability reduces, therefore not preferred.

In order to promote the curing reaction of hydroxyl, carboxyl and isocyanate group, can in photosensitive polymer combination of the present invention, add urethane catalyzer.As urethane catalyzer, preferably use and be selected from tin series catalysts, metal chloride, metal acetylacetonate salt, metal sulfate, amines or/and the more than a kind urethane catalyzer in the group of amine salt composition.

As aforementioned tin series catalysts, for example, can list the organo-tin compound such as stannous octoate, dibutyl tin laurate, inorganic tin compound etc.

As aforementioned metal chloride, can list the chloride of the metal being formed by Cr, Mn, Co, Ni, Fe, Cu or Al, such as cobaltic chloride, nickel chloride, iron chloride etc.

As aforementioned metal acetylacetonate, can list the acetylacetonate of the metal being formed by Cr, Mn, Co, Ni, Fe, Cu or Al, such as acetylacetone cobalt, nickel acetylacetonate, ferric acetyl acetonade etc.

As aforementioned metal sulfate, can list the sulfate of the metal being formed by Cr, Mn, Co, Ni, Fe, Cu or Al, such as copper sulphate etc.

As aforementioned amines, for example, can list existing known triethylenediamine, N, N, N ', N '-tetramethyl-1,6-hexane diamine, two (2-dimethyl aminoethyl) ether, N, N, N ', N ", N " '-five methyl diethylentriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholine base diethyl ether, N-methylimidazole, dimethyl aminopyridine, triazine, N '-(2-hydroxyethyl)-N, N, N '-trimethyl-bis-(2-amino-ethyl) ether, N, N-Exxal8 amine, N, N-dimethylamino ethoxy ethanol, N, N, N '-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N-(2-hydroxyethyl)-N, N ', N ", N " '-tetramethyl diethylene triamine, N-(2-hydroxypropyl)-N, N ', N ", N " and-tetramethyl diethylene triamine, N, N, N '-trimethyl-N '-(2-hydroxyethyl) propane diamine, N-methyl-N '-(2-hydroxyethyl) piperazine, two (N, N-dimethylaminopropyl) amine, two (N, N-dimethylaminopropyl) isopropanolamine, 2-amino quinine ring, 3-amino quinine ring, 4-amino quinine ring, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1-(2 '-hydroxypropyl) imidazoles, 1-(2 '-hydroxypropyl)-glyoxal ethyline, 1-(2 '-hydroxyethyl) imidazoles, 1-(2 '-hydroxyethyl)-glyoxal ethyline, 1-(2 '-hydroxypropyl)-glyoxal ethyline, 1-(3 '-aminopropyl) imidazoles, 1-(3 '-aminopropyl)-glyoxal ethyline, 1-(3 '-hydroxypropyl) imidazoles, 1-(3 '-hydroxypropyl)-glyoxal ethyline, N, N-dimethylaminopropyl-N '-(2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ', N '-bis-(2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ', N '-bis-(2-hydroxypropyl) amine, N, N-dimethyl aminoethyl-N ', N '-bis-(2-hydroxyethyl) amine, N, N-dimethyl aminoethyl-N ', N '-bis-(2-hydroxypropyl) amine, melamine and/or benzoguanamine etc.

As aforementioned amine salt, for example, can list the amine salt of the acylate system of DBU (1,8-diaza-dicyclo [5.4.0] hendecene-7) etc.

The ratio that the compounding amount of aforementioned urethane catalyzer is common amount is fully, for example, with respect to aforementioned carboxyl urethane resin 100 mass parts that contain, be preferably 0.1 ~ 20 mass parts, more preferably 0.5 ~ 10.0 mass parts.

While stating before use the Thermocurable composition in molecule with multiple ring-types (sulphur) ether, preferably contain thermal curing catalyst.As this thermal curing catalyst, for example, can list imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-the cyano ethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole; Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, the amines such as N-dimethyl benzyl amine; The hydrazine compound such as adipic dihydrazide, sebacic dihydrazide; The phosphorus compounds such as triphenylphosphine etc.In addition, as commercially available product, for example can list 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound) that Shikoku Chem manufactures, U-CAT (registered trademark) 3503N, U-CAT3502T (being the trade name of the blocked isocyanate compounds of dimethylamine) that SAN-APRO Ltd. manufactures, DBU, DBN, U-CATSA 102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc.Particularly be not limited to these compounds, as long as the thermal curing catalyst of epoxy resin thermosetting catalyzer, oxetane compound or promote epoxy radicals and/or the material reacting of oxa-cyclobutyl and carboxyl, can use separately or by two or more mixing use.In addition, can also use guanamines, methyl guanamines, benzoguanamine, melamine, 2,4-diamido-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid addition product, 2, the Striazine derivatives such as 4-diamido-6-methacryloxyethyl-s-triazine isocyanuric acid addition product, the compound and the aforementioned hot curing catalysts that preferably these are also played to the effect of adaptation imparting agent are used in combination.

The compounding amount of these thermal curing catalysts as long as the ratio of common amount be sufficient, for example, with respect to aforementioned Thermocurable composition 100 mass parts containing thering is multiple ring-types (sulphur) ether in carboxyl urethane resin or molecule, be preferably 0.1 ~ 20 mass parts, more preferably 0.5 ~ 15.0 mass parts.

Photosensitive polymer combination of the present invention can compounding colorant.As colorant, can use red, blue, green, yellow etc. usual known colorant, can be any of pigment, dyestuff, pigment.Particularly, can list with following such color index (C.I.; The Society of Dyers and Colourists, Britain dyers learn distribution) material of sequence number.Wherein, from alleviating the viewpoint of carrying capacity of environment and the impact on human body, preferably not halogen-containing.

Red stain:

As red stain, have that monoazo system, bisdiazo (disazo) are, azo lake system, benzimidazolone Xi, perylene system, diketopyrrolopyrrolecocrystals system, condensation azo system, anthraquinone system, quinacridone etc., particularly, can list following material.

Monoazo system: paratonere 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269.

Bisdiazo system: pigment red 37,38,41.

Monoazo color lake system: pigment red 4 8:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57:1,58:4,63:1,63:2,64:1,68.

Benzimidazolone system: paratonere 171, paratonere 175, paratonere 176, paratonere 185, paratonere 208.

Perylene system: solvent of red 135, solvent red 179, pigment red 123, pigment red 149, paratonere 166, paratonere 178, pigment red179, paratonere 190, paratonere 194, paratonere 224.

Diketopyrrolopyrrolecocrystals system: paratonere 254, paratonere 255, paratonere 264, paratonere 270, paratonere 272.

Condensation azo system: paratonere 220, paratonere 144, paratonere 166, pigment red 21 4, paratonere 220, paratonere 221, paratonere 242.

Anthraquinone system: paratonere 168, paratonere 177, pigment red 21 6, solvent red 149, solvent red 150, solvent red 52, solvent red 207.

Quinacridone: pigment red 122, paratonere 202, paratonere 206, Pigment Red 207, paratonere 209.

Blue colorant:

As blue colorant, there are phthalocyanine system, anthraquinone system, pigment system is the compound that is classified as pigment (pigment), particularly, can list pigment blue 15, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 16, pigment blue 60.

As dyestuff system, can use solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc.Except above-mentioned, can also use metal to replace or unsubstituted phthalocyanine compound.

Green colourant:

As green colourant, there are equally phthalocyanine system, anthraquinone Xi, perylene system, particularly, can use pigment Green 7, pigment green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 etc.Except above-mentioned, can also use metal to replace or unsubstituted phthalocyanine compound.

Yellow colorants:

As yellow colorants, there are monoazo system, bisdiazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone system etc., particularly, can list following colorant.

Anthraquinone system: solvent yellow 16 3, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202.

Isoindolinone system: pigment yellow 110, pigment yellow 109, pigment yellow 13 9, pigment yellow 17 9, pigment yellow 185.

Condensation azo system: pigment yellow 93, pigment yellow 94, pigment yellow 95, pigment Yellow 12 8, pigment yellow 155, pigment yellow 166, pigment yellow 180.

Benzimidazolone system: pigment Yellow 12 0, pigment yellow 151, pigment yellow 154, pigment yellow 156, pigment yellow 17 5, pigment yellow 181.

Monoazo system: pigment yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183.

Bisdiazo system: pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198.

In addition,, in order to regulate tone, also can add the colorants such as purple, orange, dark brown, black.

If illustrate particularly, there is pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73, C.I. pigment brown 23, C.I. pigment brown 25, C.I. pigment black 1, C.I. pigment black 7 etc.

The compounding ratio of foregoing colorant is not particularly limited, and containing carboxyl urethane resin 100 mass parts, is preferably the ratio of 0 ~ 10 mass parts with respect to aforementioned, and the ratio that is particularly preferably 0.1 ~ 5 mass parts is sufficient.

Photosensitive polymer combination of the present invention can use the photosensitive compounds in molecule with multiple ethylenically unsaturated groups.It is to be irradiated and carried out photocuring by active energy beam, makes aforementioned insoluble or contribute to its insoluble material in aqueous alkali containing carboxyl urethane resin.As such compound, can use usual known polyester (methyl) acrylate, polyethers (methyl) acrylate, carbamate (methyl) acrylate, carbonic ester (methyl) acrylate, epoxy (methyl) acrylate etc., particularly, can list the acrylic acid hydroxyalkyl acrylate classes such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate; The diacrylate class of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; N,N-DMAA, N hydroxymethyl acrylamide, N, the acrylic amides such as N-dimethylaminopropyl acrylamide; Acrylic acid N, N-dimethylamino ethyl ester, acrylic acid N, the acrylic-amino alkyl esters such as N-dimethylamino propyl ester; The multicomponent methacrylate class of the polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their ethylene oxide adduct, propylene oxide adduct or 6-caprolactone addition product etc.; The multicomponent methacrylate class of ethylene oxide adduct or the propylene oxide adduct etc. of phenoxy group acrylate, bisphenol a diacrylate and these phenols; The multicomponent methacrylate class of the glycidol ethers such as glycerine diglycidyl ether, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester; Be not limited to above-claimed cpd, also can list by direct acroleic acid esterifications of polyvalent alcohol such as polyether glycol, PCDL, C-terminal polybutadiene, polyester polyols or via diisocyanate and carry out urethane acrylate and the esters of acrylic acid and the melamine acrylate that obtain, and/or the various methyl acrylic esters corresponding with aforesaid propylene acid esters etc.

And then, can enumerate that the polyfunctional epoxy resins such as cresols phenolic resin varnish type epoxy resin of sening as an envoy to react with acrylic acid and the hydroxyl of the Epocryl that obtains, this Epocryl further reacts with half carbamate compounds of the diisocyanate such as hydroxy acrylate and isophorone diisocyanate such as pentaerythritol triacrylate and epoxy amino formic ether acrylate compounds of obtaining etc.This epoxy acrylate is that resin can improve photo-curable and can not make dry to touch reduce.

In the present invention, particularly from the viewpoint of low warpage properties, bending property, can compatibly use the multicomponent methacrylate classes such as polyvalent alcohol or their ethylene oxide adduct, propylene oxide adduct or 6-caprolactone addition product, the multicomponent methacrylate such as ethylene oxide adduct or the propylene oxide adduct class of phenols, and containing the oligourethane class of (methyl) acrylate.

With respect to aforementioned, containing carboxyl urethane resin 100 mass parts, the compounding amount in this molecule with the compound of multiple ethylenically unsaturated groups is the ratio of 5 ~ 100 mass parts, more preferably the ratio of 5 ~ 70 mass parts.In the situation of aforementioned compounding amount lower than 5 mass parts, photo-curable reduces, and is difficult to develop to form pattern by the postradiation alkali of active energy beam, therefore not preferred.On the other hand, exceed in the situation of 100 mass parts, the dissolubility of aqueous alkali is reduced, film becomes fragile, therefore not preferred.

In order to improve physical strength of its film etc., photosensitive polymer combination of the present invention is compounding filler as required.As such filler, can use known usual inorganic or organic filler, particularly preferably use barium sulphate, preparing spherical SiO 2 and talcum.And then, in order to obtain white outward appearance, anti-flammability, can also use the metal oxides such as titanium dioxide, metal hydroxides as extender pigment filler.With respect to aforementioned carboxyl urethane resin 100 mass parts that contain, the compounding amount of these fillers is preferably below 300 mass parts, and more preferably 0.1 ~ 200 mass parts, is particularly preferably 1 ~ 100 mass parts.The compounding amount of filler exceedes in the situation of 300 mass parts, and the viscosity of composition uprises, and printing reduces, and solidfied material becomes fragile, therefore not preferred.

And then in order to improve dry to touch, to improve treatability etc., photosensitive polymer combination of the present invention can use binder polymer.For example, can use polyester based polymer, polyurethane series polymkeric substance, polyester urethane based polymer, polyamide-based polymkeric substance, polyesteramide based polymer, acrylic acid series polymeric compounds, cellulose-based polymkeric substance, polymer in poly lactic acid series, phenoxy group based polymer etc.These binder polymers can use separately or can be used as potpourri of more than two kinds and use.

And then in order to give flexibility, to improve the fragility of solidfied material etc., photosensitive polymer combination of the present invention can use elastic body.For example, can use polyester based elastomers, polyurethane series elastic body, polyester urethane based elastomers, polyamide-based elastic body, polyesteramide based elastomers, acrylic elastomer, ethylene series elastic body.In addition, also can use and part or all epoxy radicals of the epoxy resin with various skeletons be carried out to resin of modification etc. with the carboxyl acid modified type butadiene-propylene of two ends nitrile rubber.And then also can use containing the polybutadiene based elastomers of epoxy radicals, the polybutadiene based elastomers containing acryloyl group, polybutadiene based elastomers, the isoprene based elastomers of hydroxyl etc. of hydroxyl.These elastic bodys can use separately or use as potpourri of more than two kinds.

And then, for synthetic aforementioned containing carboxyl urethane resin, prepare composition, or in order to adjust viscosity to be applied in substrate, carrier film, photosensitive polymer combination of the present invention can be with an organic solvent.

As this organic solvent, can list ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, petroleum solvent etc.More specifically, be the ketone such as MEK, cyclohexanone; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; The glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monomethyl ether; The ester classes such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether acetic acid esters; The alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; The aliphatic hydrocarbon such as octane, decane; The petroleum solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc.Such organic solvent can use separately or use as potpourri of more than two kinds.

Generally speaking, macromolecular material is Once you begin oxidized mostly, will constantly cause the oxidative degradation of linksystem, thereby cause the function of macromolecular material to reduce, therefore photosensitive polymer combination of the present invention, for anti-oxidation, also can add the radical scavenger that produced free radical was lost efficacy or/and be the antioxidants such as harmless material and the peroxide decomposer that does not produce new free radical by produced peroxide breakdown.Particularly using while using antioxidant in butadiene-based elastomer compositions used in the present invention, PCT patience promotes, and peeling off when HAST, variable color tails off, and is effective.

The antioxidant working as radical scavenger, as concrete compound, can list quinhydrones, 4-tert-butyl catechol, TBHQ, p methoxy phenol, 2, 6-di-t-butyl-paracresol, 2, 2-methylene-bis-(4-methyl-6-tert-butylphenol), 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1, 3, 5-tri-(3 ', 5 '-di-tert-butyl-4-hydroxyl benzyl)-guanamine, 4, 6-(1H, 3H, 5H) the phenol such as triketone system, p methoxy phenol, the quinone based compounds such as benzoquinones, two (2, 2, 6, 6-tetramethyl-4-piperidyl)-sebacate, the amine compounds such as phenothiazine etc.

Radical scavenger can be commercially available product, for example can list ADK STAB (registered trademark) AO-30, ADK STAB AO-330, ADK STAB AO-20, ADKSTAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STABLA-68, (be above ADEKA Corporation manufactures ADK STAB LA-87, trade name), IRGANOX (registered trademark) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, (be above Ciba Japan K.K manufactures TINUVIN 5100, trade name) etc.

The antioxidant working as peroxide decomposer, as concrete compound, can list the phosphorus series compounds such as triphenyl phosphite, pentaerythrite four lauryl sulfo-acrylate, dilauryl thiodipropionate, distearyl-3, the chalcogenide compounds such as 3 '-thiodipropionate etc.

Peroxide decomposer can be commercially available product, (ADEKA Corporation manufactures for example can to list ADK STABTPP, trade name), Mark AO-412S (Adeka Argus Chemical Co., Ltd. manufacture, trade name), Sumizier (registered trademark) TPS (Sumitomo Chemical Co manufacture, trade name) etc.

Above-mentioned antioxidant can be used alone a kind or use combination of more than two kinds.

In addition, generally speaking, macromolecular material absorbs light, and generation decomposition is deteriorated thus, and therefore, in order to take for ultraviolet stabilization countermeasure, photosensitive polymer combination of the present invention, except using above-mentioned antioxidant, can use ultraviolet light absorber.

As ultraviolet light absorber; can list benzophenone derivates, benzoate derivatives, benzotriazole derivatives, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate derivates, Anthranilate derivant, dibenzoyl methane derivant etc.As the object lesson of benzophenone derivates, can list ESCALOL 567, Octabenzone, 2,2 '-dihydroxy-4-methoxy benzophenone and 2,4-DihydroxyBenzophenone etc.As the object lesson of benzoate derivatives, can list BMDBM, phenyl salicytate, salicylic acid to tert-butyl-phenyl ester, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester and cetyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester etc.As the object lesson of benzotriazole derivatives, can list 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole and 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole etc.As the object lesson of pyrrolotriazine derivatives, can list hydroxyphenyltriazinuv, Tinosorb S etc.

As ultraviolet light absorber, it can be commercially available product, for example can list TINUVINPS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN405, TINUVIN 460, TINUVIN 479 (above for Ciba Japan K.K manufactures, trade name) etc.

Above-mentioned ultraviolet light absorber can use separately a kind or two or more is used in combination, and by using with aforementioned antioxidant combination, can realize the stabilization of the molding being obtained by photosensitive polymer combination of the present invention.

In order to improve light sensitivity, photosensitive polymer combination of the present invention can be used as known usual N phenylglycine class, phenoxy acetic acids, sulfo-phenoxy acetic acids, thyroidan of chain-transferring agent etc.If enumerate the object lesson of chain-transferring agent, for example, there are mercapto succinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, halfcystine, thiosalicylic acid and derivant thereof etc. to there is the chain-transferring agent of carboxyl; Mercaptoethanol, mercaprol, Mercaptobutanol, mercapto-propanediol, sulfydryl butylene glycol, hydroxy benzenes mercaptan and derivant thereof etc. have the chain-transferring agent of hydroxyl; 1-butyl mercaptan, 3-mercaptopropionic acid butyl ester, 3-mercapto-propionate, 2,2-(ethylidene dioxy base) diethyl mercaptan, ethyl mercaptan, 4-methylbenzene mercaptan, lauryl mercaptan, propanethiol, butyl mercaptan, amyl hydrosulfide, 1-spicy thioalcohol, cyclopentanethiol, cyclohexylmercaptan, thioglycerol, 4,4-thiobis benzenethiol etc.

In addition, can use multi-functional mercaptan based compound, there is no particular limitation as to it, for example can use hexane-1,6-bis-mercaptan, decane-1, the analiphatic sulphur alcohols such as 10-bis-mercaptan, dimercapto diethyl ether, dimercapto diethyl thioether, xylylene two mercaptan, 4, the aromatic mercaptans classes such as 4 '-dimercapto diphenyl sulfide, Isosorbide-5-Nitrae-dimercaptobenzene; Poly-(mercaptoacetate) class of the polyvalent alcohols such as ethylene glycol bis (mercaptoacetate), polyglycol two (mercaptoacetate), propylene glycol two (mercaptoacetate), glycerine three (mercaptoacetate), trimethylolethane trimethacrylate (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrite four (mercaptoacetate), dipentaerythritol six (mercaptoacetate); Poly-(3-mercaptopropionic acid ester) class of the polyvalent alcohols such as ethylene glycol bis (3-mercaptopropionic acid ester), polyglycol two (3-mercaptopropionic acid ester), propylene glycol two (3-mercaptopropionic acid ester), glycerine three (3-mercaptopropionic acid ester), trimethylolethane trimethacrylate (mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester); Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl acyloxy) butane, 1,3,5-tri-(sulfydryl butoxyethyl group)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketones, pentaerythrite four (3-sulfydryl butyric ester) etc. gather (sulfydryl butyric ester) class.

As their commercially available product, for example can list BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC (is Sakai Chemical Industry Co. above, Ltd. manufacture), Karenz (registered trademark) MT-PE1, Karenz MT-BD 1 and Karenz-NR1 (above for Showa Denko K. K manufactures) etc.

And then, work as chain-transferring agent, there is the heterogeneous ring compound of sulfydryl, for example, can list sulfydryl-4-butyrolactone (another name: 2-sulfydryl-4-butyrolactone), 2-sulfydryl-4-methyl-4-butyrolactone, 2-sulfydryl-4-ethyl-4-butyrolactone, 2-sulfydryl-4-sulfo-butyrolactone, 2-sulfydryl-4-butyrolactam, N-methoxyl-2-sulfydryl-4-butyrolactam, N-ethoxy-2-sulfydryl-4-butyrolactam, N-methyl-2-sulfydryl-4-butyrolactam, N-ethyl-2-sulfydryl-4-butyrolactam, N-(2-methoxyl) ethyl-2-sulfydryl-4-butyrolactam, N-(2-ethoxy) ethyl-2-sulfydryl-4-butyrolactam, 2-sulfydryl-5-valerolactone, 2-sulfydryl-5-valerolactam, N-methyl-2-sulfydryl-5-valerolactam, N-ethyl-2-sulfydryl-5-valerolactam, N-(2-methoxyl) ethyl-2-sulfydryl-5-valerolactam, N-(2-ethoxy) ethyl-2-sulfydryl-5-valerolactam, 2-mercaptobenzothiazole, 2-sulfydryl-5-methyl mercapto-thiadiazoles, 2-sulfydryl-6-caprolactam, (three associations change into Co., Ltd. and manufacture 2,4,6-tri-thiol-s-triazine: trade name Zisnet F), trade name Zisnet DB) and 2-anilino--4 2-dibutylamino-4, (three associations change into Co., Ltd. and manufacture 6-dimercapto-s-triazine:, (three associations change into Co., Ltd.'s manufacture to 6-dimercapto-s-triazine: trade name Zisnet AF) etc.

As heterogeneous ring compound chain-transferring agent, that there is sulfydryl that belongs to the developability of not damaging photosensitive polymer combination, particularly preferably mercaptobenzothiazoler, 3-sulfydryl-4-methyl-4H-1,2,4-triazole, 5-methyl isophthalic acid, 3,4-thiadiazoles-2-mercaptan, 1-phenyl-5-sulfydryl-1H-TETRAZOLE.These chain-transferring agents can use separately or two or more is used in combination.

In order to improve the adaptation of interlayer or the adaptation of raising photo-sensitive resin and base material, photosensitive polymer combination of the present invention can use closely sealed promoter.Concrete example, for example, have benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: the Accel M that chemical industry Co., Ltd. of Kawaguchi manufactures), 3-morpholino methyl isophthalic acid-phenyl-triazole-2-thioketones, 5-amino-3-morpholino methyl-thiazole-2-thioketones, 2-sulfydryl-5-methyl mercapto-thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole, contain amino benzotriazole, silane coupling agent etc.

Photosensitive polymer combination of the present invention can further add the thixotroping agents such as fine particle silica, organobentonite, smectite, hydrotalcite as required.From the ageing stability as thixotroping agent, preferably organobentonite, hydrotalcite.Particularly hydrotalcite has excellent electrical characteristics.In addition, can the hot polymerization inhibitor of compounding, defoamer and/or the levelling agents such as silicon-type, fluorine system, macromolecular, the silane coupling agents such as imidazoles system, thiazole system, triazole system, the known usual additive kinds such as copper inhibitor such as rust preventive and bis-phenol system, triazine thiol system.

Aforementioned hot polymerization inhibitor can for prevent the thermal polymerization of aforementioned polymerizable compound or through time polymerization.As hot polymerization inhibitor, for example can list 4-metoxyphenol, quinhydrones, the quinhydrones that alkyl or aryl replaces, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, 2-dihydroxy benaophenonel, 4-methoxyl-2-dihydroxy benaophenonel, stannous chloride, phenothiazine, chloranil, naphthylamines, betanaphthol, 2, 6-di-t-butyl-4-cresols, 2, 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitro benzene, picric acid (picric acid), 4-toluidine, methylene blue, the reactant of copper and organic sequestering agent, gaultherolin, and phenothiazine, nitroso compound, the chelate of nitroso compound and Al etc.

Photosensitive polymer combination of the present invention is for example adjusted to aforementioned organic solvent the viscosity that is suitable for coating process, be applied on base material by methods such as dip coating, flow coat method, rolling method, scraper rubbing method, silk screen print method, curtain Tu Fa, by the organic solvent volatile dry (temporarily dry) comprising make composition at the temperature of approximately 60 ~ 100 ℃ in, can form not snearing film.Then, adopt contact (or cordless) to make active energy beam carry out selectivity exposure or carry out direct pattern exposure by the direct exposure machine of laser by forming figuratum photomask, for example, by aqueous alkali (0.3 ~ 3% aqueous sodium carbonate) unexposed portion is developed, thereby form corrosion-resisting pattern.And then, in situation for the composition that contains Thermocurable composition, for example make its heat curing by the temperature that is heated to approximately 140 ~ 180 ℃, the aforementioned carboxyl containing carboxyl urethane resin is reacted with the Thermocurable composition in molecule with multiple ring-type ethers and/or cyclic thioether base, can form the cured coating film of each excellents such as thermotolerance, chemical-resistant, resistance to hydroscopicity, adaptation, electrical specification.In addition, even not containing Thermocurable composition in the situation that, by thermal treatment, also can time carry out hot radical polymerization with the ethylenic unsaturated bond of the residual photo-curable composition of unreacted state to exposure, improve coating characteristic, therefore,, according to object/purposes, can heat-treat (heat curing).

As above-mentioned base material, except being pre-formed the printed circuit board (PCB), flexible printed circuit board of circuit, also can make the copper-clad laminated board of all grades (FR-4 etc.) that the compound substances such as paper using-phenolics, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth/nonwoven fabrics-epoxy resin, glass cloth/paper-epoxy resin, synthon-epoxy resin, fluororesin tygon PPO cyanate make, Kapton, PET film, glass substrate, ceramic substrate, wafer board etc.

Being coated with the volatile dry carrying out after photosensitive polymer combination of the present invention can use heated air circulation type drying oven, IR stove, hot plate, convective oven case etc. (use has the equipment of the thermal source of the air heat mode of utilizing steam, makes the method for the hot air convection contact in dryer and is blown into the mode on supporter by nozzle) to carry out.

As following, be coated with after photosensitive polymer combination of the present invention volatile dry, to obtained film expose (irradiation of active energy beam).The exposure portion (part of being irradiated by active energy beam) of film solidifies.

Irradiate the exposure machine using as above-mentioned active energy beam, can use direct describing device (for example, by utilize Direct Laser to draw the laser direct imaging device of image from the cad data of computing machine), be equipped with metal halide lamp exposure machine, be equipped with (surpassing) high-pressure sodium lamp exposure machine, be equipped with the exposure machine of mercury short-arc lamp or use the direct describing device of the UV-lamp such as (surpassing) high-pressure sodium lamp.As active energy beam, as long as use the laser of maximum wavelength within the scope of 350 ~ 410nm, can be any of gas laser, Solid State Laser.In addition, its exposure according to thickness etc. and different, is generally 5 ~ 300mJ/cm ², be preferably 5 ~ 200mJ/cm ².As above-mentioned direct describing device, for example, can use Orbotech Ltd. manufacture, PENTAX

The device of CORPORATION manufacture etc., produces the device of maximum wavelength at 350 ~ 410nm laser as long as vibrating, can use any device.

As aforementioned developing method, can utilize infusion process, shower method, spray-on process, spread coating etc., as developer solution, can use the aqueous alkalis such as potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine.

Except the method being directly coated with on base material with liquid state, photosensitive polymer combination of the present invention can also with have solder mask dry film form use, this solder mask is coated with solder resist be dried and forms in advance on the films such as polyethylene terephthalate.Below show the situation of photosensitive polymer combination of the present invention as dry film that use.

Dry film has the structure strippable cover film of carrier film, solder mask and use as required being stacked gradually and form.Solder mask is the layer that the photosensitive polymer combination of alkali-developable is coated with and is dried and obtain on carrier film or cover film.Can obtain as follows dry film: in carrier film, form after solder mask thereon stacked cover film or on cover film, form solder mask, this duplexer is stacked in carrier film.

As carrier film, can use the thermoplastic films such as the mylar of 2 ~ 150 μ m thickness.

Solder mask is by knife type coater, lip coating machine, comma coating machine, film coated machine etc., alkali-developable photosensitive resin composition to be evenly coated with and to be dried on carrier film or cover film with the thickness of 10 ~ 150 μ m to form.

As cover film, can use polyethylene film, polypropylene film etc., but cover film is less than the cohesive force of carrier film and solder mask with the cohesive force of solder mask.

In order to use dry film to make diaphragm (permanent diaphragm) on printed circuit board (PCB), peel off cover film, solder mask is overlapping with the base material that is formed with circuit, and use laminating machine etc. is fitted, and on the base material that is formed with circuit, forms solder mask.Similarly the solder mask forming is exposed, develops, is heating and curing with aforementioned, can form cured coating film.Carrier film can be exposed front again or be exposed and peel off afterwards afterwards.

Embodiment

Below provide embodiment and comparative example illustrates the present invention, but the invention is not restricted to following embodiment.Wherein, following " part " and " % " all refer to quality criteria if not otherwise specified.

Synthesis example 1

Be provided with stirring apparatus, in the flask of recirculatory pipe, add as in 1 molecule, have multiple epoxy radicals epoxy resin Nippon Kayaku K. K manufacture NC-3000 (epoxide equivalent 255g/eq.) 300.0g, as the acrylic acid 84.7g of monocarboxylic acid in molecule with ethylenically unsaturated group, as 2 of hot polymerization inhibitor, 6-di-tert-butyl-4-methy phenol 1.8g, as the triphenylphosphine 1.8g of catalysts, as propylene glycol monomethyl ether (PGMEA) 207.2g of reaction dissolvent, reaction at 98 ℃ of temperature of reaction until reactant liquor acid number reach below 1mgKOH/g, obtain the epoxy carbonate of hydroxyl.

Then, the reactant liquor 335.5g of the epoxy carbonate that input contains obtained hydroxyl, as the dimethylolpropionic acid 60.7g containing carboxylic diol compound, as 2 of fatty family diisocyanate cpd, 4,4-trimethyl hexamethylene diisocyanate 104.1g, as the PGMEA88.7g of reaction dissolvent, at 80 ℃ of temperature of reaction, react, and reach time point below 0.1% as reaction end using NCO content, obtain having biphenyl backbone containing carboxyl urethane resin (being referred to as below varnish 1).The acid number of solid constituent 65% resin is 60mgKOH/g.

Varnish 2:

In comparative example 1, use containing carboxy resin be used the Bisphenol F structure that contains photonasty group multi-functional epoxy's base containing carboxyl photoresist, the ZFR-1124 (solid constituent 63%, the acid number of resin is 102mgKOH/g) that Nippon Kayaku K. K manufactures.

Varnish 3:

What in comparative example 2, use is to have used the multi-functional epoxy's of the bis-phenol structure that contains photonasty group photonasty to contain carboxy resin containing carboxy resin, the ZCR-1601 (solid constituent 65%, the acid number of resin is 98mgKOH/g) that Nippon Kayaku K. K manufactures.

Varnish 4:

What in comparative example 3, use is that the photonasty with carbamic acid ester structure that contains photonasty group contains carboxy resin containing carboxy resin, is the P7B-53 (solid constituent 53%, the acid number of resin is 49mgKOH/g) that Kyoeisha Chemical Co., Ltd. manufactures.

The preparation of aluminium hydroxide slurry:

Using aluminium hydroxide (Showa Denko K. K manufacture Higilite 42M) 700g and carbitol acetic acid esters 295g, Ricinate 5g mix and blend as solvent, and use the zirconium oxide bead of 0.5 μ m to carry out dispersion treatment with bowl mill.This operation is repeated 3 times, and by the filtrator of 3 μ m, thereby aluminium hydroxide slurry made.

The modulation of silica slurry:

By spherical silicon dioxide (ADMATECHS CO., LTD. the SO-E2 manufacturing) 700g, as the carbitol acetic acid esters 295g of solvent, as the vinyl silicane coupling agent 5g mix and blend of silane coupling agent, and similarly with bowl mill, obtained material is carried out to dispersion treatment with above-mentioned.This operation is repeated 3 times, and filter with the filtrator of 3 μ m, thereby made silica slurry.

Embodiment 1 ~ 14, comparative example 1 ~ 3

Use the resin solution of above-mentioned synthesis example, carry out compounding with the various compositions shown in the ratio shown in table 1 and table 2 (mass parts) his-and-hers watches 1 and table 2, with after stirring machine premixed, carry out with triple-roller mill mixing, thereby prepared solder resist photosensitive polymer combination., by the granulometry of grinding meter (grindmeter) that utilizes ERICHSEN company to manufacture, the dispersion degree of obtained photosensitive polymer combination is evaluated, result is below 15 μ m herein.

[table 1]

[table 2]

Optimum exposure:

After by the circuit pattern of thick copper 18 μ m, for substrate, buffing roll (buffing roll) grinds, wash and be dried, then utilize silk screen print method that the whole face of photosensitive polymer combination of above-described embodiment 1 ~ 14 and comparative example 1 ~ 3 is coated on described substrate, with the heated air circulation type kiln drieds of 80 ℃ 30 minutes.After dry, use the exposure device (HMW-680-GW20) that is equipped with metal halide lamp, be situated between and exposed by stage metraster (Kodak No.2), will develop (30 ℃, 0.2MPa, 1wt%Na ₂cO ₃aqueous solution) the exposure when pattern of residual stage metraster is 6 sections 60 seconds times is as optimum exposure.

Evaluating characteristics:

Utilize serigraphy that the whole face of each composition of above-described embodiment 1 ~ 14 and comparative example 1 ~ 3 is coated on the Kapton substrate that is formed with circuit pattern or Kapton100H (TorayDupont CO., LTD. the Kapton of manufacturing, thickness 25 μ m) on, at 80 ℃, be dried 30 minutes, be cooled to room temperature.On obtained substrate, use the exposure device (HMW-680-GW20) that is equipped with metal halide lamp with optimum exposure, solder resist pattern to be exposed, with the 1wt%Na of 30 ℃ ₂cO ₃aqueous solution was developed for 60 seconds under the condition of spray pressure 0.2MPa, obtained corrosion-resisting pattern.This substrate is heated to 60 points at 150 ℃ to be cured.Obtained printed base plate (evaluation substrate) is carried out to following evaluating characteristics.

The resistance to sweating heat performance of < >

On the evaluating characteristics substrate of making, be coated with rosin series solder flux on the Kapton substrate that is formed with circuit pattern, and be immersed in the welding groove that is redefined for 260 ℃, with after modification alcohol cleaning solder flux, peel off and evaluate by the visual expansion to resist layer.Determinating reference is as follows.

Flood zero: 1 10 seconds, do not find to peel off.

△: flood 15 second, does not find to peel off.

×: flood 15 second, has resist layer to expand, peel off.

The gold-plated property of < chemically-resistant >

Use the electroless nickel bath of commercially available product and chemical gilding to bathe, under the condition of nickel 3 μ m, golden 0.03 μ m, carry out plating, by tape stripping evaluate resist layer have or not peel off, plating solution has or not infiltration, then, evaluate resist layer by tape stripping and have or not and peel off.Criterion is as follows.

Zero: observe infiltration, peel off.

△: confirming after plating has slight infiltration, and after tape stripping, nothing is peeled off.

×: after plating, peel off.

< low warpage properties >

Cut 50 × 50mm from the curing overlay film of making at Kapton 100H, measure the warpage at 4 angles and obtain mean value, evaluate according to following benchmark.

Zero: warpage is lower than 0 ~ 3mm.

△: warpage is more than 3mm and lower than 7mm.

×: warpage is more than 7mm.

< bending property >

Using the curing overlay film of making on Kapton 100H, bend, there is the number of times before crackle in record.

< anti-flammability >

Utilize serigraphy that whole the composition of each embodiment and comparative example face is coated on to the Kapton that 25 μ m are thick (Kapton 100H) and the thick Kapton (Kapton 50H) of 12.5 μ m is upper, dryly at 80 ℃ after 20 minutes, be cooled to room temperature.And then, similarly, with whole coating back side of serigraphy, at 80 ℃, be dried and be cooled to room temperature after 20 minutes, thereby obtain double spread substrate.On obtained double spread substrate, use the exposure device (HMW-680-GW20) that is equipped with metal halide lamp, with optimum exposure, solder resist is carried out to whole exposure, with the 1wt%Na of 30 ℃ ₂cO ₃aqueous solution was developed for 60 seconds under the condition of spray pressure 0.2MPa, then at 150 ℃, carried out heat curing in 60 minutes, made assess sample.For this anti-flammability sample for evaluation, carry out the thin material testing vertical flammability based on UL94 specification.Evaluate based on UL94 specification, represent with VTM-0 or VTM-1.

Table 3, table 4 are summed up and be shown in to the result of aforementioned each evaluation test.

[table 3]

[table 4]

From result shown in table 3, the flexible PCB of embodiment 1 ~ 14 has sufficient low warpage properties, bending property with solder resist, and has excellent anti-flammability concurrently.On the other hand, as shown in table 4, comparative example is very difficult to realize the balance of low warpage properties, bending property and anti-flammability.

Therefore known, according to the present invention, can obtain having concurrently whole photosensitive polymer combination of low warpage properties, bending property, anti-flammability.

Embodiment 15 ~ 28

The composition MEK of removing in previous embodiment 1 ~ 14 after silicon-type defoamer is diluted, and be coated on PET film, at 80 ℃, be dried 30 minutes, thereby form the photosensitive polymer combination layer of thickness 20 μ m.And then the cover film of fitting is thereon made dry film, respectively as embodiment 15 ~ 28.Peel off cover film from obtained dry film, to forming heat lamination film on figuratum copper clad laminate, then, under the condition same with the substrate using in the coating characteristic evaluation of previous embodiment, expose.After exposure, peel off carrier film, press in spray under the condition of 0.2MPa, with the 1wt%Na of 30 ℃ ₂cO ₃aqueous solution is carried out the development in 60 seconds, obtains corrosion-resisting pattern.This substrate is heating and curing 60 minutes at 150 ℃, by aforesaid test method and evaluation method, the obtained cured film test substrate that has is carried out to the evaluation test of each characteristic.Its result is as shown in table 5.

[table 5]

Shown in aforementioned table 3 and table 5, result can be clear and definite, photosensitive polymer combination of the present invention not only can be taken into account with low warpage properties as the resistance to welding of compromise (trade off) relation is hot, the gold-plated property of chemically-resistant, can also realize excellent bending and anti-flammability.

utilizability in industry

The use in printed circuit board photosensitive polymer combination can alkali developing of the present invention is that halogen-free composition and carrying capacity of environment are few, there is anti-flammability and low warpage, bending property excellence, therefore, as printed circuit board (PCB), particularly as TAB (tape automated bonding, the automatic combination of winding), the solder resist of flexible PCB (FPC) use of the representative such as COF (chip on film, covers brilliant film) is optimum.

Claims (6)

1. the use in printed circuit board photosensitive polymer combination can alkali developing, is characterized in that, it contains

Obtain take diol compound as raw material have xenol Novolac structure containing carboxyl urethane resin, the epoxy resin of the xenol Novolac structure of wherein said diol compound by making to have the structure that has following formula (I) reacts and obtains with monoacid

In formula, n represents mean value, is 1.01～5;

Photoepolymerizationinitiater initiater;

Aluminium hydroxide and/or organic phosphorus flame retardant.

2. photosensitive polymer combination according to claim 1, it is characterized in that, described containing carboxyl urethane resin be epoxy resin by making to have xenol Novolac structure react with monoacid the diol compound that obtains, with there is the diol compound of carboxyl, react with diisocyanate cpd obtain contain carboxyl urethane resin.

3. photosensitive polymer combination according to claim 1, is characterized in that, described Photoepolymerizationinitiater initiater comprises oxime ester compound.

4. photosensitive polymer combination according to claim 1, is characterized in that, it also contains Thermocurable composition.

5. a dry film, it is coated on film and dry obtaining by the photosensitive polymer combination described in any one in claim 1～4.

6. a printed circuit board (PCB), it has the cured film that makes photocatalytic coating film be solidified into pattern-like and to obtain, wherein, described film is the photosensitive polymer combination described in any one in claim 1～4 to be coated on base material and the film that forms, or described photosensitive polymer combination is coated on film and the dry and dry film lamination that obtains on base material and the film forming.